EP0063944B1 - Polyhydrische Alkohole - Google Patents

Polyhydrische Alkohole Download PDF

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Publication number
EP0063944B1
EP0063944B1 EP82302126A EP82302126A EP0063944B1 EP 0063944 B1 EP0063944 B1 EP 0063944B1 EP 82302126 A EP82302126 A EP 82302126A EP 82302126 A EP82302126 A EP 82302126A EP 0063944 B1 EP0063944 B1 EP 0063944B1
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Prior art keywords
group
hydroxymethyl
formula
sum
compounds
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EP82302126A
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French (fr)
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EP0063944A1 (de
Inventor
Edgar Robert Rogier
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Henkel Corp
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Henkel Corp
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Priority claimed from US06/257,674 external-priority patent/US4356128A/en
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Priority to AT82302126T priority Critical patent/ATE14212T1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C08G18/3209—Aliphatic aldehyde condensates and hydrogenation products thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C08G18/3823—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
    • C08G18/3825—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing amide groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C08G18/3838—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing cyano groups

Definitions

  • the present invention relates to polyhydric alcohols and in particular to polyhydric alcohols having a further polar functional group.
  • US Patent 4093637 in particular discloses the preparation of C 1 - s alkyl esters, such as the methyl, ethyl and butyl esters, of 9,9(10,10)-bis(hydroxymethyl) octadecanoic acid and describes these esters as being useful as intermediates in the preparation of primary plasticizers for polyvinylchloride. Further disclosure of hydroformylation technology is made in an article entitled "Obtention de derives biofunctionnels" by R. Lai in Rev. Fr. Corporation Gras. 17:455 (1970) b.
  • Such compounds however, have carboxyl groups or hydrolyzable ester groups and are thus not fully usable for wetting pigments in polyurethane coatings.
  • compounds such as those of the present invention are miscible with polyisocyanates used to formulate coating systems. It is, of course, necessary to have sufficient miscibility to allow the formulations of the polyhydroxy compounds of the present invention into polyurethanes.
  • the compounds of the present invention may be utilized in any area where both a polyhydroxyl functionality and a polar group are required.
  • polyhydroxymethyl compounds of formula I (wherein X represents a hydrogen atom or a hydroxymethyl group; M represents a cyano, ester or N,N-disubstituted amide group, the CH 2- M bond being a carbon-carbon bond; m, n, p, q, r, s and t are non-negative integers the sum of which is from 11 to 19; and n, q and s each has the value 0 or 1, the sum of n, q and s being 1, 2 or 3; with the provisos that where the sum of n, q and s is 1, X is a hydroxymethyl group, where the sum of n, q and s is 2 or 3, each group represented by X is the same and that where the sum of n, q and s is 1 and the sum of m, p, r and t is 14, M represents a cyano or N,N-disubstituted amide
  • the polar group M preferably represents a cyano group, an ester group of formula -COOR or an amide group of formula -CONR 2 (in which R may be the same or different).
  • the substituent R is an organic radical, preferably a C 1 - 4 straight chained or branched alkyl group, optionally substituted by a hydroxyl group, or a phenyl group.
  • M represents the amide group -CONR 2
  • the moiety NR 2 together may further represent a piperidino or morpholino group.
  • the sum of m, n, p, q, r, s and t preferably is from 13 to 17.
  • the integers m and t are each preferably at least 3, especially preferably 4, 5, 6 or greater. Where q is 1, it is preferred that n and s are each 0.
  • the requirement for the compound of formula I to contain at least two hydroxymethyl groups (the proviso that where the sum of n, q and s is 1, X represents a hydroxymethyl group) will be satisfied where the molecule contains a gem bis hydroxymethyl group and/or where hydroxymethyl groups are located at different carbon atoms on the carbon chain backbone of the molecule of formula I.
  • the present invention relates to polyhydroxyl compounds which contain a polar functional group which may be introduced into the molecule by one of several methods.
  • the hydroxyl functionality may be introduced into the molecule by utilizing an unsaturated material which is hydroformylated e.g. by the use of synthesis gas (a carbon monoxide/hydrogen mixture) to introduce a formyl group at the site of the unsaturation.
  • Catalysts may be selected such that a polyunsaturated material is either polyhydroformylated or is monohydroformylated.
  • Rhodium catalysts give products which introduce the formyl group at substantially every location of unsaturation in the molecule.
  • cobalt catalysts introduce a formyl group only at one site of unsaturation in conjugated polyunsaturated materials.
  • the formyl groups can then be reacted via a Tollens' reaction utilizing a strong base and two moles of formaldehyde per mole of the original formyl group, to convert the formyl group directly to the gemina/-bis(hydroxymethyl) structures.
  • the formyl group may be converted with selective catalysts such as sodium borohydride to convert the formyl group to a hydroxymethyl group. It is noted, however, that the present invention requires that if such a reaction is conducted the intermediate aldehyde must contain more than one formyl group to ensure that a polyhydroxymethyl compound will be obtained.
  • a process for the preparation of polyhydroxymethyl compounds of formula I which process comprises (a) hydroformylating an olefinic compound of formula II (wherein M is as hereinbefore defined; a, b, c, d, e, f and g are non-negative integers, the sum of a, c, e, g, 2b, 2d and 2f being from 11 to 19; and b, d and f each has the value 0 or 1, the sum of b, d and f being 1, or 3) and (b) converting the or each group in the product thereby obtained (i) to a group by reacting with formaldehyde in the presence of a strong base, (ii) to a group by catalytic reduction, or (iii) to a group by reacting with formaldehyde in the presence of a weak base and subsequently to a group be reduction, subject to the proviso that where the product obtained by step (a)
  • the starting materials of formula II which may be converted into the desired products of this invention include oleonitrile, a commercially available compound.
  • the reactions are shown in the following scheme: Cat.9(10)-formyloctadecanonitrile (I) 9,9(10,10)-bis(hydroxymethyl)octadecanonitrile
  • linoleonitrile can be converted into a tetrahydroxynitrile or a dihydroxy nitrile as shown in the following scheme:
  • linolenonitrile can be converted into the triformyl derivative by hydroformylation using a rhodium catalyst and synthesis gas.
  • a tri [gem-bis(hydroxymethyl)] octadecanonitrile can be formed by reacting triformyl nitrile with excess formaldehyde and caustic.
  • unsaturated fatty compounds having 13-23 carbon atoms excluding those in the polar substituent M
  • having the above terminal polar function can be used for the preparation of the polyhydric alcohols of formula I.
  • 9,9(10,10)-bis(hydroxymethyl)-N,N-disubstituted octadecanamide can be obtained from oleic acid as a starting material as illustrated in the following scheme:
  • R in the disubstituted amide above may be for example dimethyl, diethyl, diphenyl, dibutyl, piperidene or morpholine.
  • oleic acid is used as an example of the starting material, linoleic and linolenic acids could alternatively be used.
  • ester of oleic acid may be converted very usefully through the use of isobutylene to give the tertiary butyl ester denominated as t-butyl 9,9(10,10)-bis(hydroxymethyl)octadecanoate.
  • the t-butyl esters of linolenic and linoleic acids may also be employed analogously.
  • Another class of compounds are noted as starting materials for reacting with synthesis gas to obtain compounds having formyl groups in more than one position in the molecule.
  • This class includes linoleyl or linolenyl acids and alcohols as such starting materials are required to have more than one site of unsaturation.
  • the two or three formyl groups which result from hydroformylation of a starting material containing two or three carbon-carbon double bonds, may be reduced with sodium borohydride to obtain the di- or tri hydroxymethyl product, e.g.
  • the product will be, for instance, a 9(10), 12(13) di-hydroxymethyloctadecanonitrile, amide or ester, (such as a tertiary butyl ester).
  • R Suggested values for R are those having from 1 to 4 carbon atoms such as methyl, ethyl, propyl, butyl, sec-butyl, hydroxypropyl, hydroxyethyl or mixtures thereof, and, for the moiety NR 2 , morpholino and piperidino groups.
  • hydrogen and carbon monoxide are added in a closed vessel at temperatures of from 100 to 150 degrees C.
  • the hydrogen and carbon monoxide may be maintained conveniently at molar ratios of from 1.5:0.5to about 0.5:1.5. It is noted that the ratio is not critical so long as the pressure is maintained in the reaction vessel by the component gases and the amount of hydrogen is not so great as to substantially reduce the unsaturated starting materials.
  • hydroformylation with the synthesis gas may be conducted at from about 90 degrees C to about 170 degrees C, preferably from 110 degrees C to about 130 degrees C. Above the higher temperatures described above, increased amounts of unwanted by-products are formed in the reaction mixture.
  • the pressure conditions suitably are maintained in this sealed system at from about 20 to about 500 atmospheres (20.3 to 506.6 bar), preferably from about 30 to about 100 atmospheres absolute (30.4 to 101.3 bar) during the hydroformylation.
  • rhodium-based catalyst Conventional cobalt catalysts may be employed to obtain a single formyl group, but are not particularly suitable for polyunsaturated compounds due to reduction of the unsaturation.
  • the practical catalyst to use during the synthesis gas reaction is a rhodium-based catalyst.
  • the rhodium may be in any convenient form such as rhodium metal, rhodium oxide, and various other rhodium salts such as rhodium chloride, rhodium dicarbonyl chloride dimer, rhodium nitrate, rhodium trichloride and other similar materials.
  • the rhodium catalyst is also best utilized with a ligand such as trisubstituted phosphine or trisubstituted phosphite.
  • a ligand such as trisubstituted phosphine or trisubstituted phosphite.
  • trisubstituted includes both alkyl and aryl compounds and the substituted compounds of alkyl and aryl compounds.
  • a particularly valuable ligand for the rhodium carbonyl hydride is triphenylphosphite or triphenylphosphine in that both compounds are particularly useful in minimizing migration of the double bond thereby avoiding a large number of isomers with respect to the formyl group.
  • triarylphosphines or triarylphosphites may be used for this purpose in the formation of the rhodium carbonylhydride ligand.
  • the foregoing materials are extremely valuable in minimizing the undesired saturation of the double bond or the reduction of the formyl group.
  • materials such as sodium borohydride may be utilized to reduce the formyl group to a hydroxymethyl group thereby obtaining desired compounds of the invention.
  • formaldehyde (which is relatively inexpensive) may be used in for example up to 1.5, preferably up to 1.2 times the amount actually required to obtain the hydroxymethyl formyl or the gem-bis(hydroxymethyl) compounds.
  • a convenient manner of adding the formaldehyde and conducting the Tollens' reaction is by using a methanol solution of formaldehyde.
  • sodium hydroxide conveniently may be employed, although potassium or calcium hydroxide may alternatively be employed.
  • the Tollens' reaction is generally conducted at a temperature of from about 0 degrees to about 100 degrees C, preferably from about 20 degrees C to about 70 degrees C.
  • the compounds of the present invention are particularly suitable for use in reaction with polyisocyanates to form urethanes.
  • a substantial advantage in the compounds of the present invention is that the polar group of the molecule enhances miscibility of the respective urethane forming components.
  • Another significant advantage is the wetting ability of the polar groups which allows for the introduction of pigments such as organic or inorganic pigments, e.g. titanium dioxide, chrome yellow, calcium or barium Lithol, phthocyanines and oxide pigments thereby providing urethane coatings with a high pigment carrying capability.
  • compositions comprising a compound of formula I or the reaction product thereof with a polyisocyanate.
  • the reaction temperature is maintained between 16-27 degrees C for 20 minutes.
  • the reaction mixture is stripped under vacuum at 49 degrees C to remove methanol and water.
  • the residual product is washed at 54 degrees C with 500 millilitres of water plus 100 millilitres of saturated sodium sulfate solution.
  • the upper organic phase is separated and washed successively with 500 millilitres of 0.1 N sodium hydroxide solution and 4x with 500 millilitres portions of water.
  • the product is finally dried in partial vacuum (1 mm Hg (1.33 mbar)) at 70 degrees C.
  • the yield of crude BHMON was 832 grams.
  • Thermoplastic and thermosetting polymers are prepared as shown in the Table.
  • BHON is used to indicate 9(10) gem-bis (hydroxymethyl)octadecanonitrile.
  • MDI is methylene diisocyanate and PM 1000 is PolyMeg 1000 a polyoxytetramethylene glycol. The ratios are in equivalents.
  • BD indicates 1,4 butane diol and C-20 triol is 9(10)gem-bis(hydroxymethyl)octadecanol.
  • A is a thermoplastic elastomer and B is thermosetting elastomer.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Paints Or Removers (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Claims (9)

1. Polyhydroxymethyl-Verbindungen der Formel I
Figure imgb0027
(in der
X ein Wasserstoff-Atom oder eine Hydroxymethyl-Gruppe bezeichnet,
M eine Cyano-, Ester- oder N,N-disubstituierte Amid-Gruppe bezeichnet, wobei die CH2-M -Bindung eine Kohlenstoff-Kohlenstoff-Bindung ist,
m, n, p, q, r, s und t nicht negative ganze Zahlen sind, deren Summe 11 bis 19 beträgt, und n, q und s jeweils den Wert 0 oder 1 haben, wobei die Summe von n, q und s 1, 2 oder 3 ist, mit der Maßgabe, daß, wenn die Summe von n, q und s 1 ist, X eine Hydroxymethyl-Gruppe bezeichnet, und wenn die Summe von n, q und s 2 oder 3 ist, jede durch X bezeichnete Gruppe die gleiche ist, und daß, wenn die Summe von n, q und s 1 ist und die Summe von m, p, r und t 14 ist, M eine Cayno- oder N,N-disubstituierte Amid-Gruppe bezeichnet) und deren Gemische.
2. Verbindungen nach Anspruch 1, dadurch gekennzeichnet, daß M eine Cyano-Gruppe ist.
3. Verbindungen nach Anspruch 1, dadurch gekennzeichnet, daß M eine Gruppe -COOR oder -CONR2 ist, worin R, die beide gleich oder verschieden sein können, wenn M eine Amid-Gruppe bezeichnet, eine geradkettige oder verzweigte C1_4-Alkyl-Gruppe bezeichnet, die gegebenenfalls durch eine Hydroxyl-Gruppe oder eine Phenyl-Gruppe substituiert ist, und, wenn M eine Amid-Gruppe bezeichnet, die Gruppe -NR2 weiterhin eine Piperidino- oder Morpholino-Gruppe darstellen kann.
4. Verbindungen nach irgendeinem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß für sie wenigstens eine der folgenden Bedingungen erfüllt ist:
(a) die Summe von m, n, p, q, r, s und t beträgt 13 bis 17;
(b) q ist 1 und n und s sind jeweils 0;
(c) m und t sind jeweils 3 oder größer; und
(f) m und t sind jeweils 4 oder größer.
5. Verbindungen der Formel I nach Anspruch 1, ausgewählt aus den folgenden:
(a) 9,9(10,10)-Bis(hydroxymethyl)octadecanonitril;
(b) 9,9(10,10),12,12(13,13)-Tetra(hydroxymethyl)octadecanonitril;
(c) 9,9(10,10),12,12(13,13),15,15(16,16)-Hexa(hydroxymethyl)octadecanonitril;
(d) 9(10),12(13)-Di(hydroxymethyl)octadecanonitril und
(e) 9(10),12(13),15(16)-Tri(hydroxymethyl)octadecanonitril.
6. Verfahren zur Herstellung von Polyhydroxymethyl-Verbindungen der Formel I (wie in Anspruch 1 definiert) durch
(a) Hydroformylieren einer olefinischen Verbindung der Formel II
Figure imgb0028
(in der
M die in Anspruch 1 angegebene Bedeutung hat,
a, b, c, d, e, f und g nicht-negative ganze Zahlen sind, wobei die Summe aus a, c, e, g, 2b, 2d und 2f 11 bis 19 beträgt und b, d, f jeweils den Wert 0 oder 1 haben, wobei die Summe von b, d und f jeweils 1, 2 oder 3 ist) und
(b) Überführen der oder jeder
Figure imgb0029
-Gruppe in dem dadurch erhaltenen Produkt
(i) in eine
Figure imgb0030
durch Reaktion mit Formaldehyd in Gegenwart einer starken Base,
(ii) in eine
Figure imgb0031
-Gruppe durch katalytische Reduktion oder
(iii) in eine
Figure imgb0032
-Gruppe durch Reaktion mit Formaldehyd in Gegenwart einer schwachen Base und anschließend in eine
Figure imgb0033
-Gruppe durch Reduktion, mit der Maßgabe, daß

wenn das in Schritt (a) erhaltene Produkt eine einzelne Formyl-Gruppe enthält, die Umwandlung des Schrittes (b) mittels der Verfahrensschritte (i) oder (iii) durchgeführt wird.
7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß die Hydroformylierung gemäß Schritt (a) in Gegenwart eines Rhodium-Katalysators durchgeführt wird.
8. Verfahren nach Anspruch 6 oder Anspruch 7, dadurch gekennzeichnet, daß die Ausgangs-Verbindung der Formel (11) eine Oleyl-, Linoleyl- oder Linolenyl-Verbindung ist.
9. Anstrichmittel oder Formmassen, enthaltend eine Verbindung der Formel nach Anspruch 1 oder deren Reaktionsprodukt mit einem Polyisocyanat.
EP82302126A 1981-04-27 1982-04-26 Polyhydrische Alkohole Expired EP0063944B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT82302126T ATE14212T1 (de) 1981-04-27 1982-04-26 Polyhydrische alkohole.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US257674 1981-04-27
US06/257,674 US4356128A (en) 1981-04-27 1981-04-27 Fatty polyhydric alcohols having a polar functional group

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EP0063944A1 EP0063944A1 (de) 1982-11-03
EP0063944B1 true EP0063944B1 (de) 1985-07-10

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Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0263192A1 (de) * 1986-10-03 1988-04-13 HENKEL CORPORATION (a Delaware corp.) Dicyanethenyl-Fettverbindungen und deren Derivate
US4626582A (en) * 1985-02-28 1986-12-02 Henkel Corporation Acryloxymethyl substituted fatty compounds
EP0266436A1 (de) * 1986-10-03 1988-05-11 HENKEL CORPORATION (a Delaware corp.) Substituierte Fettäther
CN100497288C (zh) 2003-04-25 2009-06-10 陶氏环球技术公司 由种子油制得的醛和醇组合物

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2605270A (en) * 1949-06-21 1952-07-29 Swern Daniel Amides of 9, 10-dihydroxystearic acid
FR1184093A (fr) * 1956-10-08 1959-07-16 Rohm & Haas Procédé d'hydroxylation d'acides, d'esters et de nitriles aliphatiques
US4093637A (en) * 1977-01-31 1978-06-06 The United States Of America As Represented By The Secretary Of Agriculture Alkyl 9,9(10,10)-bis(acyloxymethyl)octadecanoates as primary plasticizers for polyvinylchloride
DE3061482D1 (en) * 1979-04-04 1983-02-03 Henkel Corp Gem-bis (hydroxymethyl) alcohols and mixtures thereof with diols, process for their preparation and a process for the preparation of polyurethanes therefrom

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DE3264652D1 (de) 1985-08-14
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